Preparation Method and Application of Sluge-Al-MOF Denitrification and Mercury Removal Synergistic Catalyst Synthesized from Aluminum-Containing Sludge

Abstract

The present invention discloses a preparation method of a Sludge-Al-MOF denitrification and mercury removal synergistic catalyst synthesized from aluminum-containing sludge, comprising the following steps: dehydrating, heat-treating and drying, and pulverizing the aluminum-containing sludge in sequence to obtain aluminum-containing sludge particles; dissolving the aluminum-containing sludge particles in a chlorinating agent solution, shearing and stirring, mixing evenly, and then roasting to obtain chlorinated granular sludge; dissolving the chlorinated granular sludge in deionized water to obtain solution one; taking terephthalic acid and dissolving it in DMF and ethanol to obtain solution two; mixing solution one and solution two, and reacting under ultrasonic shearing conditions to obtain a mixed solution; performing solid-liquid separation on the mixed solution, washing and centrifuging the obtained solid, and then activating it to finally obtain an aluminum-containing sludge Sludge-Al-MOF denitrification and mercury removal synergistic catalyst. The present invention also discloses the application of the Sludge-Al-MOF denitrification and mercury removal synergistic catalyst prepared by the above preparation method. The Sludge-Al-MOF catalyst prepared by the present invention has high mercury removal and denitrification efficiency, low reaction temperature, and does not produce secondary pollution.

Description

Technical Field

[0001] The present invention belongs to the technical fields of waste aluminum-containing sludge recycling and flue gas denitrification and mercury removal, and particularly relates to a preparation method and application of a Sludge-Al-MOF denitrification and mercury removal catalyst synthesized from aluminum-containing sludge. Background Art

[0002] Thermal power generation is the main force in the development of China's electric power, consuming about 2.15 billion tons of raw coal annually, and the coal consumption of coal-fired power plants accounts for about 70%. There are many types of elements in coal (C, H, O, N, S, Hg 0 ), so during the combustion process, it will generate pollutants such as dust, NO x , SO x , Hg 0 , CO2, etc. While these pollutants cause great pressure on the atmospheric environment, they also seriously endanger the physical health of humans. As the main place with high coal consumption, coal-fired power plants have mainly treated the atmospheric pollutants generated by their combustion with soot and SO2 for many years. However, with the increasingly severe environmental situation, China has more stringent requirements for the control of pollutants such as nitrogen oxides and mercury.

[0003] In terms of mercury removal, currently, the mercury removal technologies in coal-fired power plants can be divided into three types: pre-combustion mercury removal, in-combustion mercury removal, and post-combustion flue gas mercury removal. Among them, the research on post-combustion mercury removal technology is the most extensive. Mercury in coal-fired flue gas mainly exists in three forms: particulate mercury, gaseous divalent mercury, and elemental mercury. Research shows that the relative percentage contents of mercury in the three forms in coal-fired flue gas are 56%, 34%, and 10% respectively. Elemental mercury in coal-fired flue gas is the main form, which is volatile and insoluble, and is the focus of coal-fired mercury pollution. Currently, the main flue gas mercury removal technologies include adsorbent mercury removal technology, SCR catalytic oxidation technology, photocatalytic technology, etc. The adsorption method is a coal-fired flue gas mercury removal method that has been studied more. Commonly used high-efficiency adsorbents include activated carbon, fly ash, calcium-based adsorbents, etc. Generally, the mercury removal rate of ordinary activated carbon is not ideal, and the operation cost is too high, seriously affecting the application of this technology.

[0004] In terms of denitrification, the relatively mature flue gas denitrification technology applied in industry is selective catalytic reduction technology (SCR). Its principle is to use a reducing agent (ammonia, CO, or hydrocarbon, etc.) to selectively react with NOx to generate N2 and H2O under the action of a catalyst. At the same time, a large number of studies have shown that while the SCR denitrification system promotes the reduction of NO x , it also has an impact on Hg 0It also has a certain oxidation effect. In the prior art, due to the advantages of high denitration rate, simple operation, low operation cost and no secondary pollution, the ammonia-based denitration technology is the only SCR denitration technology that can be industrialized at present. The core of the SCR denitration technology is the catalyst. At present, the vanadium-titanium catalyst is the most widely used and highly active catalyst in industry. Although it has excellent catalytic activity and application potential, there are still some obvious disadvantages: (1) Vanadium has biological toxicity and there are safety risks; (2) The temperature window is too high and the reaction mechanism is not clear; (3) It cannot efficiently meet the reduction of NO and Hg 0 oxidation.

[0005] Reducing NO x and Hg 0 for centralized treatment promotes the upgrading of end-of-pipe treatment, energy and space efficiency. This strategy is not only a reasonable choice in terms of technology and economy, but also an important direction for the development of multi-pollutant synchronous control technology. However, considering that the SCR denitration technology has a low oxidation and removal rate of Hg 0 when used for flue gas denitration, it is difficult to meet the environmental protection requirements, and the active components of the catalyst used need to be loaded on the carrier. Commonly used carriers are titanium dioxide, silica, activated carbon, etc. Such catalysts are prone to poisoning, difficult to regenerate and have high synthesis costs, making it difficult to carry out industrial applications. These problems severely restrict the practical application of traditional vanadium-based catalysts in the simultaneous removal of NOx and Hg 0 Therefore, it is urgent to develop a catalyst with a wide range of material sources, no pollution and capable of simultaneously meeting high-efficiency denitration and mercury removal for application in SCR catalytic technology. Summary of the Invention

[0006] The purpose of the present invention is to overcome the above deficiencies in the prior art, and provide a preparation method and application of a Sludge-Al-MOF denitration and mercury co-removal catalyst synthesized from aluminum-containing sludge. The prepared Sludge-Al-MOF catalyst has high mercury removal and denitration efficiency, low reaction temperature, wide temperature window, long tolerance time, low cost, high recycling times, and the product does not produce secondary pollution, and can meet the requirements of industrial application.

[0007] To achieve the above object, the technical solution adopted by the present invention is to provide a preparation method of a Sludge-Al-MOF denitration and mercury co-removal catalyst synthesized from aluminum-containing sludge, including the following steps:

[0008] Step 1: Dehydrate and heat-treat and dry the aluminum-containing sludge in sequence, and then perform a crushing treatment to obtain aluminum-containing sludge particles;

[0009] Step 2: Dissolve the aluminum-containing sludge particles obtained in Step 1 in a chlorinating agent solution, perform shear stirring, and after mixing evenly, send it into an inert atmosphere for roasting to obtain chlorinated granular sludge;

[0010] Step 3: Take the chlorinated granular sludge in Step 2 as a substrate and dissolve it in deionized water to obtain Solution 1;

[0011] Step 4: Take terephthalic acid as an organic ligand and dissolve it in DMF and ethanol to obtain Solution 2;

[0012] Step 5: Mix Solution 1 in Step 3 and Solution 2 in Step 4, and react under ultrasonic shearing conditions to obtain a uniformly dispersed and uniformly sized mixed solution;

[0013] Step 6: Perform solid-liquid separation on the mixed solution in Step 5, wash the obtained solid with DMF and ethanol, centrifuge it, then activate it using freeze-drying technology, and finally grind and screen it to obtain an aluminum-containing sludge Sluge-Al-MOF denitrification and mercury removal synergistic catalyst.

[0014] Further, the heat treatment in Step 1 is carried out in a muffle furnace, the temperature of the heat treatment is 80 - 200 °C, and the crushing is carried out in a ball mill.

[0015] Further, the chlorinating agent solution in Step 2 is an HCl solution and / or an NH4Cl solution, the shear stirring in Step 2 is carried out in a shear reactor, the shear speed is 20 - 60 r / min, and the shear time is 5 - 20 min.

[0016] Further, the inert atmosphere in Step 2 is N2 or Ar, the roasting temperature in Step 2 is 100 - 300 °C, and the roasting time is 1 - 3 h.

[0017] Further, the mass ratio of chlorinated granular sludge to terephthalic acid in the mixed solution in Step 5 is 1:1 - 1:3.

[0018] Further, the ultrasonic power in Step 5 is 20 - 100 W, and the ultrasonic time is 5 - 20 min.

[0019] Further, the shear speed in Step 5 is 20 - 60 r / min, and the shear time is 5 - 20 min.

[0020] Further, the washing method in Step 6 is to wash 3 times with ethanol and DMF respectively.

[0021] Further, the activation temperature in Step 6 is -20 °C to -50 °C, and the activation reaction time is 2 - 8 h.

[0022] The present invention also provides an application of a Sludge-Al-MOF denitrification and mercury co-removal catalyst prepared by the above preparation method, and the Sludge-Al-MOF denitrification and mercury co-removal catalyst is used for denitrification and mercury removal of coal-fired flue gas.

[0023] The present invention has the following advantages compared with the prior art:

[0024] 1. The Sludge-Al-MOF catalyst prepared by the present invention has high mercury and denitrification efficiency, low reaction temperature, wide temperature window, long tolerance time, low cost, high cycle times, and the product does not cause secondary pollution, and can meet the requirements of industrial application.

[0025] 2. The solid waste-based Sludge-Al-MOF material prepared by the present invention contains a large number of unsaturated metal active sites, which is beneficial to enhancing the adsorption of pollutants NO x and Hg 0 during the reaction process, thereby promoting the forward progress of the catalytic reaction. At the same time, the organic ligands in the solid waste-based Sludge-Al-MOF material contain functional groups, which can serve as active sites for the catalytic reaction.

[0026] 3. The Sludge-Al-MOF catalyst prepared by the present invention is a metal-organic framework material MOF with aluminum-containing sludge as the metal node. It has a very high specific surface area, which is beneficial to the reaction of reactant molecules with the catalyst surface. At the same time, the structure and components of MOF can be regulated by design and synthesis. Therefore, the catalyst can be customized to adapt to different reaction conditions and catalytic reaction types. Based on the characteristics of MOF materials such as high surface area, tunability, multifunctionality, and renewability, the pore size, shape, and surface properties can be controlled by design and synthesis, so as to be used in various catalytic reactions with a wide range of applications.

[0027] 4. The present invention uses aluminum-containing sludge in sewage as the substrate aluminum source to replace the traditional aluminum salt, realizing the resource utilization of solid waste, reducing the production cost, and being able to be used in industrial applications, with certain economic benefits.

[0028] 5. The solid waste-based Sludge-Al-MOF material prepared by the present invention is synthesized in an ultrasonic shear reaction kettle. Under the double coupling conditions of ultrasonic and shear, the reaction time is greatly shortened and the production cost is reduced.

[0029] 6. In the present invention, a chlorinating agent solution is added to the aluminum-containing sludge, and halogen groups are grafted onto the catalyst itself to directionally regulate the coupling of halogen and metal ions, realizing the efficient removal of mercury under low-chlorine and chlorine-free conditions.

[0030] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Description of the Drawings

[0031] Figure 1 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the first embodiment of the present invention.

[0032] Figure 2 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the second embodiment of the present invention.

[0033] Figure 3 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the third embodiment of the present invention.

[0034] Figure 4 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the fourth embodiment of the present invention.

[0035] Figure 5 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the fifth embodiment of the present invention.

[0036] Figure 6 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the sixth embodiment of the present invention.

[0037] Figure 7 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the seventh embodiment of the present invention.

[0038] Figure 8 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the eighth embodiment of the present invention.

[0039] Figure 9 It is a schematic diagram of the denitrification and mercury removal efficiency of the denitrification and mercury co-removal catalyst prepared in the ninth embodiment of the present invention. Detailed Embodiments

[0040] Embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although some embodiments of the present invention are shown in the drawings, it should be understood that the present invention can be implemented in various forms and should not be construed as limited to the embodiments set forth herein. On the contrary, these embodiments are provided to more thoroughly and completely understand the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not used to limit the protection scope of the present invention.

[0041] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in conjunction with the embodiments.

[0042] AsFigures 1-9 As shown, the present invention provides a preparation method of a Sluge-Al-MOF denitrification and mercury co-removal catalyst synthesized from aluminum-containing sludge, comprising the following steps:

[0043] Step 1: The aluminum-containing sludge is dehydrated, heat-treated and dried in sequence, and then pulverized in a ball mill to obtain aluminum-containing sludge particles. The heat treatment in this step is carried out in a muffle furnace, and the heat treatment temperature is 80-200°C. The aluminum-containing sludge is derived from municipal sludge;

[0044] Step 2: The aluminum-containing sludge particles obtained in Step 1 are dissolved in HCl solution and / or NH4Cl solution, and shearing and stirring are carried out in a shearing reactor. The shearing speed is 20-60 r / min and the shearing time is 5-20 min. After mixing evenly, it is sent into an inert atmosphere of N2 or Ar and calcined at a calcination temperature of 100-300°C and a calcination time of 1-3 h to obtain chlorinated granular sludge. In this step, since the removal of mercury overly relies on strongly oxidizing gases such as HCl gas, and the oxidation effect is limited under chlorine-free and low-chlorine conditions, therefore, in a conventional SCR catalytic reaction, a trace amount of HCl gas is introduced, and the HCl gas has strong oxidizing property and has a certain corrosive effect on the SCR equipment. Since the strongly oxidizing halogen group promotes the conversion of Hg 0 to Hg 2+ in flue gas, therefore, in this step, a chlorinating agent solution is added to the aluminum-containing sludge, aiming to graft halogen groups on the catalyst itself, directionally regulate the coupling of halogen and metal ions, and achieve efficient removal of mercury under low-chlorine and chlorine-free conditions;

[0045] Step 3: The chlorinated granular sludge in Step 2 is used as a substrate and dissolved in deionized water to obtain Solution 1;

[0046] Step 4: Take terephthalic acid as an organic ligand and dissolve it in DMF and ethanol to obtain Solution 2;

[0047] Step 5: Mix Solution 1 in Step 3 and Solution 2 in Step 4, and react under ultrasonic shearing conditions. The ultrasonic power is 20 - 100 W, the ultrasonic time is 5 - 20 min, the shearing rotation speed is 20 - 60 r / min, and the shearing time is 5 - 20 min to obtain a uniformly dispersed mixture with consistent particle sizes. The mass ratio of chlorinated granular sludge to terephthalic acid in the mixture is 1:1 - 1:3. In this step, since the synthesis of MOFs is a self-assembly reaction of metal substrates and organic ligands, Solution 1 serves as the metal substrate and Solution 2 serves as the organic ligand. They are mixed and reacted in a reaction kettle at a certain temperature and time for the purpose of self-assembly reaction to synthesize MOF. Conventional Al-MOF is reacted in a polytetrafluoroethylene reaction kettle, generally requiring a reaction temperature of 24 h and a reaction temperature of 180 °C, with a long reaction time, high cost, and low catalyst yield. However, the synthesis of the solid waste-based Sludge-Al-MOF in this step is carried out in an ultrasonic shearing reaction kettle. Under the dual coupling conditions of ultrasonic and shearing, the reaction time is only 5 - 20 min, greatly shortening the reaction time and reducing the production cost.

[0048] Step 6: Place the mixture in Step 5 in a beaker, let it stand for precipitation and then perform solid-liquid separation. Wash the obtained solid with DMF and ethanol 3 times respectively, centrifuge it, and then activate it using freeze-drying technology. The activation temperature is -20 °C to -50 °C, and the activation reaction time is 2 - 8 h. Finally, grind and sieve it to obtain the aluminous sludge Sludge-Al-MOF denitrification and mercury removal catalyst.

[0049] The present invention also provides an application of an aluminous sludge for synthesizing the Sludge-Al-MOF denitrification and mercury removal catalyst, and the Sludge-Al-MOF denitrification and mercury removal catalyst is used for denitrification and mercury removal of coal-fired flue gas.

[0050] Example 1

[0051] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 200 °C, and then crush it using a ball mill to obtain aluminum-containing sludge particles. Then, measure 30 mL of HCl solution, dissolve the aluminum-containing sludge particles in 30 mL of HCl solution, and place them in a shear reactor and shear for 10 min at 40 r / min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under N2 inert conditions and perform calcination in a tube furnace at a calcination temperature of 200 °C and a calcination time of 2 h to obtain chlorinated granular sludge; Weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 50 W and an ultrasonic time of 10 min and a shear condition with a shear speed of 40 r / min and a time of 10 min to obtain a uniformly dispersed and uniformly sized mixture; Perform solid-liquid separation on the mixture. The obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, activated in freeze-drying at -30 °C for 6 h, and finally ground and sieved to obtain an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 1 shown.

[0052] Example 2

[0053] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 200 °C, and then crush it using a ball mill to obtain aluminum-containing sludge particles. Then, measure 30 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 30 mL of NH4Cl solution, and place them in a shear reactor and shear for 10 min at 40 r / min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under N2 inert conditions and perform calcination in a tube furnace at a calcination temperature of 200 °C and a calcination time of 2 h to obtain chlorinated granular sludge; Weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 50 W and an ultrasonic time of 10 min and a shear condition with a shear speed of 40 r / min and a time of 10 min to obtain a uniformly dispersed and uniformly sized mixture; Perform solid-liquid separation on the mixture. The obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, activated in freeze-drying at -30 °C for 6 h, and finally ground and sieved to obtain an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 2 shown.

[0054] Example 3

[0055] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 200 °C, and then use a ball mill to crush it to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear for 10 min at 40 r / min to uniformly disperse and react the aluminum-containing sludge. Then, place the above mixture under N2 inert conditions and perform roasting in a tubular furnace at a roasting temperature of 200 °C for 2 h to obtain chlorinated granular sludge; weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 50 W and an ultrasonic time of 10 min and shear conditions with a shear speed of 40 r / min and a time of 10 min to obtain a uniformly dispersed and homogeneous mixture with consistent particle size; perform solid-liquid separation on the mixture. After the obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, it is activated in a freeze dryer at -30 °C for 6 h, and finally, after grinding and sieving, an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles is obtained. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 3 shown.

[0056] Example 4

[0057] Weigh 2 g of aluminum-containing sludge, heat-treat it in a muffle furnace at a temperature of 200 °C, then crush it using a ball mill to obtain aluminum-containing sludge particles. Further, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear at 40 r / min for 10 min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under N2 inert conditions and calcine it in a tubular furnace at a calcination temperature of 200 °C and a calcination time of 2 h to obtain chlorinated granular sludge; Weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 80 W and an ultrasonic time of 20 min and a shear condition with a shear speed of 40 r / min and a time of 10 min to obtain a uniformly dispersed and uniformly sized mixed liquid; Separate the solid and liquid of the mixed liquid. After the obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, it is activated in a freeze dryer at -30 °C for 6 h, and finally ground and sieved to obtain an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitrification and mercury co-removal catalytic reaction, and the results are as Figure 4 shown.

[0058] Example 5

[0059] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 200 °C, and then use a ball mill to crush it to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear at 40 r / min for 10 min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under N2 inert conditions and calcine it in a tube furnace at a calcination temperature of 200 °C for 2 h to obtain chlorinated granular sludge; Weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 80 W and an ultrasonic time of 20 min and shear conditions with a shear speed of 50 r / min and a time of 20 min to obtain a uniformly dispersed and homogeneous mixture with consistent particle size; Separate the solid and liquid of the mixture. After the obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, it is activated in a freeze dryer at -30 °C for 6 h, and finally, after grinding and sieving, an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles is obtained. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 5 shown.

[0060] Example 6

[0061] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 200 °C, and then use a ball mill to crush it to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear at 40 r / min for 10 min to make the aluminum-containing sludge evenly disperse and react. Then, place the above mixture under N2 inert conditions and calcine it in a tubular furnace at a calcination temperature of 200 °C and a calcination time of 2 h to obtain chlorinated granular sludge; weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under ultrasonic conditions with an ultrasonic power of 80 W and an ultrasonic time of 20 min and shear conditions with a shear speed of 50 r / min and a time of 20 min to obtain a uniformly dispersed and homogeneous mixture with consistent particle size; perform solid-liquid separation on the mixture. After the obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, it is activated in a freeze dryer at -30 °C for 6 h, and finally, after grinding and sieving, an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles is obtained. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 6 shown.

[0062] Example 7

[0063] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 80 °C, then crush it using a ball mill to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear at 20 r / min for 5 min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under an Ar inert condition and calcine it in a tubular furnace at a calcination temperature of 100 °C and a calcination time of 1 h to obtain chlorinated granular sludge; weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1, weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2, mix Solution 1 and Solution 2, and react under ultrasonic conditions with an ultrasonic power of 20 W and an ultrasonic time of 5 min and shear conditions with a shear speed of 20 r / min and a time of 5 min to obtain a uniformly dispersed and uniformly sized mixed solution, where the mass ratio of chlorinated granular sludge to terephthalic acid in the mixed solution is 1:1; perform solid-liquid separation on the mixed solution, wash the obtained solid 3 times with 30 mL of ethanol and 30 mL of DMF respectively, activate it in a freeze dryer at -20 °C for 2 h, and finally grind and screen it to obtain an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 7 shown.

[0064] Example VIII

[0065] Weigh 2 g of aluminum-containing sludge, perform heat treatment in a muffle furnace at a temperature of 120 °C, then use a ball mill to crush it to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution, dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear at 45 r / min for 15 min to make the aluminum-containing sludge evenly disperse and react. Then, place the above mixture under an Ar inert condition and perform calcination in a tubular furnace at a calcination temperature of 150 °C for 1.5 h to obtain chlorinated granular sludge; weigh 1 g of chlorinated granular sludge as a substrate, dissolve it in deionized water to obtain Solution 1, weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2, mix Solution 1 and Solution 2, and react under an ultrasonic condition with an ultrasonic power of 60 W and an ultrasonic time of 15 min and a shear condition with a shear speed of 30 r / min and a time of 15 min to obtain a uniformly dispersed and uniformly sized mixed solution, where the mass ratio of chlorinated granular sludge to terephthalic acid in the mixed solution is 1:2; perform solid-liquid separation on the mixed solution, wash the obtained solid 3 times with 30 mL of ethanol and 30 mL of DMF respectively, activate it in a freeze dryer at -40 °C for 5 h, and finally grind and screen it to obtain an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 8 shown.

[0066] Example 9

[0067] Weigh 2 g of aluminum-containing sludge. After heat treatment in a muffle furnace at a temperature of 160 °C, it is pulverized using a ball mill to obtain aluminum-containing sludge particles. Then, measure 15 mL of HCl solution and 15 mL of NH4Cl solution. Dissolve the aluminum-containing sludge particles in 15 mL of HCl solution and 15 mL of NH4Cl solution, and place them in a shear reactor to shear for 20 min at 60 r / min to make the aluminum-containing sludge uniformly disperse and react. Then, place the above mixture under an Ar inert condition and calcine it in a tubular furnace. The calcination temperature is 300 °C and the calcination time is 3 h to obtain chlorinated granular sludge; Weigh 1 g of chlorinated granular sludge as a substrate and dissolve it in deionized water to obtain Solution 1. Weigh 1 g of terephthalic acid and dissolve it in DMF and ethanol to obtain Solution 2. Mix Solution 1 and Solution 2 and react under an ultrasonic condition with an ultrasonic power of 100 W and an ultrasonic time of 18 min and a shear condition with a shear speed of 60 r / min and a time of 18 min to obtain a uniformly dispersed and homogeneous-sized mixed solution. The mass ratio of chlorinated granular sludge to terephthalic acid in the mixed solution is 1:3; Perform solid-liquid separation on the mixed solution. After the obtained solid is washed 3 times with 30 mL of ethanol and 30 mL of DMF respectively, it is activated in a freeze dryer at -50 °C for 8 h. Finally, after grinding and sieving, an aluminum-containing sludge Sluge-Al-MOF catalyst with 50-mesh microparticles is obtained. Apply the aluminum-containing sludge Sluge-Al-MOF catalyst to the SCR denitration and mercury co-removal catalytic reaction, and the results are as Figure 9 shown.

[0068] As described above, it is only a preferred embodiment of the present invention and does not impose any limitation on the present invention. Any simple modification, change, and equivalent structural transformation made to the above embodiments according to the technical essence of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A preparation method of a denitrification and mercury co-removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge, characterized in that, It includes the following steps: Step 1: Dehydrate and heat-treat the aluminum-containing sludge successively, then perform pulverization treatment to obtain aluminum-containing sludge particles; Step 2: Dissolve the aluminum-containing sludge particles obtained in Step 1 in a chlorinating agent solution, where the chlorinating agent solution is an HCl solution and / or an NH4Cl solution, and perform shear stirring. After mixing evenly, send it into an inert atmosphere for roasting to obtain chlorinated granular sludge; Step 3: Take the chlorinated granular sludge in Step 2 as a substrate and dissolve it in deionized water to obtain Solution 1; Step 4: Take terephthalic acid as an organic ligand and dissolve it in DMF and ethanol to obtain Solution 2; Step 5: Mix Solution 1 in Step 3 and Solution 2 in Step 4, and react under ultrasonic shear conditions to obtain a uniformly dispersed mixture with consistent particle sizes; Step 6: Perform solid-liquid separation on the mixture in Step 5. Wash the obtained solid with DMF and ethanol respectively, centrifuge it, then activate it using freeze-drying technology, and finally perform grinding and sieving to obtain the aluminum-containing sludge Sluge-Al-MOF denitrification and mercury removal synergistic catalyst.

2. The preparation method of a denitrification and mercury removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 1, characterized in that, The heat treatment in Step 1 is carried out in a muffle furnace, the temperature of the heat treatment is 80 - 200 °C, and the pulverization is carried out in a ball mill.

3. The preparation method of a denitrification and mercury co-removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 1, characterized in that, The shear stirring in Step 2 is carried out in a shear reactor, the shear speed is 20 - 60 r / min, and the shear time is 5 - 20 min.

4. The preparation method of a denitrification and mercury removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 3, characterized in that, The inert atmosphere in Step 2 is N2 or Ar, the roasting temperature in Step 2 is 100 - 300 °C, and the roasting time is 1 - 3 h.

5. The preparation method of a denitrification and mercury co-removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 1, characterized in that, The mass ratio of the chlorinated granular sludge to terephthalic acid in the mixture in Step 5 is 1:1 - 1:

3.

6. The preparation method of a denitrification and mercury co-removal catalyst of Sludge-Al-MOF synthesized from aluminum-containing sludge according to claim 5, characterized in that, The ultrasonic power in Step 5 is 20 - 100 W, and the ultrasonic time is 5 - 20 min.

7. The preparation method of a denitrification and mercury co-removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 6, characterized in that, The shear speed in Step 5 is 20 - 60 r / min, and the shear time is 5 - 20 min.

8. The preparation method of a denitrification and mercury co-removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 1, characterized in that, The washing method in Step 6 is to wash 3 times with ethanol and DMF respectively.

9. The preparation method of a denitrification and mercury removal catalyst for synthesizing Sluge-Al-MOF from aluminum-containing sludge according to claim 8, characterized in that, The activation temperature in Step 6 is -20 °C to -50 °C, and the activation reaction time is 2 - 8 h.

10. Use of the aluminum-containing sludge Sluge-Al-MOF denitrification and mercury co-removal catalyst prepared by the preparation method according to any one of claims 1-9, characterized in that, The Sluge-Al-MOF denitrification and mercury removal synergistic catalyst is used for denitrification and mercury removal of coal-fired flue gas.

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